The invention belongs to preparation and application of a catalyst, and particularly relates to a double-layer catalyst and preparation thereof, and application of the catalyst in preparation of pyromellitic dianhydride. The preparation method comprises the following steps: respectively weighing effective quantities of active components (V2O5, TiO2, P2O5, Na2O, MoO3 and Sb2O3), compounds of other metals and whiskers, preparing solutions, preparing spraying slurry, spraying the slurry on a support, roasting, cooling and carrying out other technical steps to obtain catalysts E and G; respectively putting the catalysts G and E at a raw material gas mixture inlet end and a reaction gas outlet end; and preparing the pyromellitic dianhydride under the conditions of low air speed, low temperature and the like. The invention solves the problems of high operating condition requirements, massive product impurities, heavy color, low purity and the like, and has the advantages of low operating condition requirements, high product purity, fewer impurities and the like.